Nonaqueous electrolyte composition and nonaqueous electrolyte secondary battery

ABSTRACT

A nonaqueous electrolyte composition includes: a nonaqueous solvent; an electrolyte salt; a matrix resin; a filler; and a surfactant.

CROSS REFERENCES TO RELATED APPLICATIONS

This present application is a Continuation Application of patentapplication Ser. No. 12/662,291, filed Apr. 9, 2010, which claimspriority from Japanese Patent Applications JP 2009-108064 filed in theJapanese Patent Office on Apr. 27, 2009, the entire contents of whichbeing incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a nonaqueous electrolyte compositionand a nonaqueous electrolyte secondary battery.

In more detail, the present invention relates to a nonaqueouselectrolyte composition containing a nonaqueous solvent, an electrolytesalt, a matrix resin, a filler and a surfactant and a nonaqueouselectrolyte secondary battery using the same.

Also, in more detail, the present invention relates to a nonaqueouselectrolyte composition containing a nonaqueous solvent, an electrolytesalt, a matrix resin and a filler containing a prescribed aluminum oxideand a nonaqueous electrolyte secondary battery using the same.

2. Description of the Related Art

In recent years, a number of portable electronic appliances haveappeared, and it is contrived to achieve downsizing and weight reductionthereof.

Also, in batteries which are used as a power source of a portableelectronic appliance, for the purpose of realizing downsizing and weightreduction of the portable electronic appliance, it is demanded todownsize the battery itself and efficiently use a housing space withinthe portable electronic appliance.

It is known that as a battery which meets such demands, a lithium ionsecondary battery having a large energy density is the most suitable.

As such a lithium ion secondary battery, for example, one using alaminated film for an exterior member is put into practical use in viewof the facts that it is lightweight and has a high energy density andthat a battery having an extremely thin shape can be manufactured andthe like.

In a battery using a laminated film as an exterior member, for thepurposes of achieving the resistance to liquid leakage and the like, itis performed to apply, as an electrolyte, an electrolytic solution and amatrix resin for holding the electrolytic solution therein, and such abattery is known as a polymer battery.

In such a polymer battery, a degree of shape freedom is largely enhancedby using an aluminum laminated film for the exterior member. On theother hand, there is a possibility that the strength is insufficient sothat when a strong force is impressed due to the misuse, deformation iseasy to occur.

In that case, so far as such a polymer battery is covered by a firmexterior pack, there is no problem. However, in recent years, followingthe requirement for realizing a high capacity, the exterior pack becomessimple; and when the deformation is large, a short circuit is easilygenerated in the inside of the battery, resulting in bringing apossibility that the resultant does not work as a battery.

In order to cope with such problems, there has hitherto been proposed abattery obtained by coating a ceramic on the surface of an electrode(see, for example, JP-A-10-214640).

SUMMARY OF THE INVENTION

However, in the battery disclosed in JP-A-10-214640, though the strength(load) until a short circuit is generated can be increased, impregnationproperties of the electrolytic solution into an electrode is easilylowered, and as a result, there is a concern that batterycharacteristics are remarkably lowered.

The present invention addresses the above-identified and other problemsassociated with conventional technologies.

It is desirable to provide a nonaqueous electrolyte composition capableof increasing a strength (load) until a short circuit is generatedwithout remarkably lowering battery characteristics, or capable ofenhancing battery characteristics without remarkably lowering a strength(load) until a short circuit is generated, and a nonaqueous electrolytesecondary battery using the same.

In order to achieve such a desire, the present inventors made extensiveand intensive investigations.

As a result, it has been found that the foregoing desire can be achievedby forming a nonaqueous electrolyte so as to contain a matrix resin, afiller and a surfactant or to contain a matrix resin and a fillercontaining a prescribed aluminum oxide, leading to accomplishment ofembodiments according to the present invention.

That is, a nonaqueous electrolyte composition according an embodiment ofthe present invention is a composition containing a nonaqueous solvent,an electrolyte salt, a matrix resin, a filler and a surfactant.

Also, a nonaqueous electrolyte composition according to anotherembodiment of the present invention is a composition containing anonaqueous solvent, an electrolyte salt, a matrix resin and a fillercontaining at least an aluminum oxide, wherein the aluminum oxide is analuminum oxide having an alpha-conversion rate of 80% or more.

Furthermore, a nonaqueous electrolyte secondary battery according tostill an embodiment of the present invention is a battery including apositive electrode, a negative electrode, a separator and a nonaqueouselectrolyte composition, wherein the nonaqueous electrolyte compositionis a composition containing a nonaqueous solvent, an electrolyte salt, amatrix resin, a filler and a surfactant.

Moreover, a nonaqueous electrolyte secondary battery according to yetanother embodiment of the present invention is a battery including apositive electrode, a negative electrode, a separator and a nonaqueouselectrolyte composition, wherein the nonaqueous electrolyte compositionis a composition containing a nonaqueous solvent, an electrolyte salt, amatrix resin and a filler containing at least an aluminum oxide; and thealuminum oxide is an aluminum oxide having an alpha-conversion rate of80% or more.

According to the embodiments of the present invention, since thenonaqueous electrolyte is formed so as to contain a matrix resin, afiller and a surfactant or to contain a matrix resin and a fillercontaining a prescribed aluminum oxide, both high battery characteristicand high short-circuit load characteristics can be made compatible witheach other. That is, according to the embodiments of the presentinvention, a nonaqueous electrolyte composition capable of increasing astrength (load) until a short circuit is generated without remarkablylowering battery characteristics, or capable of enhancing batterycharacteristics without remarkably lowering a strength (load) until ashort circuit is generated, and a nonaqueous electrolyte secondarybattery using the same can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an exploded perspective view showing an example of anonaqueous electrolyte secondary battery according to an embodiment ofthe present invention.

FIG. 2 is a schematic sectional view along an II-II line of a batteryelement shown in FIG. 1.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Each mode for carrying out the present invention (hereinafter referredto as “embodiment”) is hereunder described. The explanation is made inthe following order.

1. First Embodiment (an example of the first nonaqueous electrolytecomposition)2. Second Embodiment (an example of the second nonaqueous electrolytecomposition)3. Third or Fourth Embodiment (an example of the first or secondnonaqueous electrolyte secondary battery)

1. First Embodiment

The first nonaqueous electrolyte composition according to the FirstEmbodiment is a composition containing a nonaqueous solvent, anelectrolyte salt, a matrix resin, a filler and a surfactant and issuitably used for a nonaqueous electrolyte secondary battery.

[Nonaqueous Solvent]

A variety of high-dielectric solvents and low-viscosity solvents can beused as the nonaqueous solvent.

As the high-dielectric solvent, a solvent containing ethylene carbonateand propylene carbonate can be exemplified as a suitable example, but itshould not be construed that the high-dielectric solvent is limitedthereto.

Examples of the high-dielectric solvent include cyclic carbonates suchas butylene carbonate, vinylene carbonate, 4-fluoro-1,3-dioxolan-2-one(fluoroethylene carbonate), 4-chloro-1,3-dioxolan-2-one (chloroethylenecarbonate) and trifluoromethylethylene carbonate.

Also, as the high-dielectric solvent, lactones such as γ-butyrolactoneand γ-valerolactone; lactams such as N-methylpyrrolidone; cycliccarbamates such as N-methyloxazolidinone; sulfone compounds such astetramethylene sulfone; and the like can be used in place of or togetherwith the cyclic carbonate.

On the contrary, examples of the low-viscosity solvent include chaincarbonates such as dimethyl carbonate, ethyl methyl carbonate, diethylcarbonate and methyl propyl carbonate; chain carboxylic acid esters suchas methyl acetate, ethyl acetate, methyl propionate, ethyl propionate,methyl butyrate, methyl isobutyrate, methyl trimethylacetate and ethyltrimethylacetate; chain amides such as N,N-dimethylacetamide; chaincarbamates such as methyl N,N-diethylcarbamate and ethylN,N-diethylcarbomate; and ethers such as 1,2-dimethoxyethane,tetrahydrofuran, tetrahydropyran and 1,3-dioxolane.

The foregoing high-dielectric solvent and low-viscosity solvent can beused singly or as an arbitrary mixture of two or more kinds thereof.

Also, a content of the nonaqueous solvent is preferably from 70 to 90%by mass. When the content of the nonaqueous solvent is less than 70% bymass, there is a concern that the viscosity excessively increases,whereas when it exceeds 90% by mass, it may be impossible to obtainsufficient conductivity.

[Electrolyte Salt]

As the electrolyte salt, any material is useful so far as it isdissolved or dispersed in the foregoing nonaqueous solvent to generatean ion, and lithium hexafluorophosphate (LiPF₆) can be suitably used.However, needless to say, it should not be construed that theelectrolyte salt is limited thereto.

For example, inorganic lithium salts such as lithium tetrafluoroborate(LiBF₄), lithium hexafluoroarsenate (LiAsF₆), lithiumhexafluoroantimonate (LiSbF₆), lithium perchlorate (LiClO₄) and lithiumtetrachloroaluminate (LiAlCl₄); lithium salts of perfluoroalkanesulfonicacid derivatives such as lithium trifluoromethanesulfonate (LiCF₃SO₃),lithium bis(trifluoromethanesulfone)imide (LiN(CF₃SO₂)₂), lithiumbis(pentafluoroethanesulfone) methide (LiC(C₂F₅SO₂)₂) and lithiumtris(trifluoromethanesulfone)methide (LiC(CF₃SO₂)₃); and the like areuseful. These lithium salts can be used singly or as an arbitrarymixture of two or more kinds thereof.

A content of the electrolyte salt is preferably from 10 to 30% by mass.When the content of the electrolyte salt is less than 10% by mass, itmay be impossible to obtain sufficient conductivity, whereas when itexceeds 30% by mass, there is a concern that the viscosity excessivelyincreases.

[Matrix Resin]

The matrix resin is not particularly limited so far as it is able toimpregnate therewith or hold therein the foregoing nonaqueous solvent,the foregoing electrolyte salt, the following filler and the followingsurfactant. For example, polymers (that is, homopolymers, copolymers andmulti-component copolymers) containing, as a constituent component,vinylidene fluoride, hexafluoropropylene, polytetrafluoroethylene, etc.are preferable. Specific examples thereof include polyvinylidenefluoride (PVdF), a polyvinylidene fluoride-hexafluoropropylene copolymer(PVdF-HFP) and a polyvinylidenefluoride-hexafluoropropylene-chlorotrifluoroethylene copolymer(PVdF-HFP-CTFE).

The matrix resin includes a matrix resin which impregnates therewith orholds therein the foregoing nonaqueous solvent and electrolyte salt,thereby causing swelling, gelation or immobilization. Also, according tothis, the liquid leakage of the nonaqueous electrolyte in the obtainedbattery can be suppressed.

Also, a content of the matrix resin is preferably from 4 to 15% by mass.In the case where the content of the matrix resin is less than 4% bymass, it may be impossible to gelate the nonaqueous electrolytecomposition, and it may be impossible to uniformly hold the fillertherein. On the other hand, in the case where the content of the matrixresin exceeds 15% by mass, there is a possibility that the batterycharacteristics are affected, for example, the energy density isreduced.

[Filler]

A variety of inorganic fillers and organic fillers can be used as thefiller.

Such a filler is desirably a ceramic powder in which a concentration ofthe total sum of impurities such as iron, copper, silicon, sodium,magnesium and zirconium (however, in the case where the ceramic powdercontains zirconium oxide, zirconium is excluded; and in the case wherethe ceramic power contains magnesium oxide, magnesium is excluded) isnot more than 100 ppm. In the case where the concentration of the totalsum of the impurities exceeds 100 ppm, there is a concern that the cyclecharacteristic in the battery characteristics is lowered.

Examples of the inorganic filler include ceramic powders such asaluminum oxide (Al₂O₃), zirconium oxide (ZrO₂), titanium oxide (TiO₂)and magnesium oxide (MgO). These ceramic powders can be used singly oras an arbitrary mixture of two or more kinds thereof.

As the aluminum oxide, for example, it is preferable to use an aluminumoxide having an alpha-conversion rate of 80% or more. When thealpha-conversion rate of the aluminum oxide is 80% or more, the batterycharacteristics can be more enhanced.

On the contrary, the organic filler is not particularly limited so faras it has a high strength in the copresence of a nonaqueous solvent ascompared with the matrix resin. Examples thereof include resin powerssuch as PTFE (polytetrafluoroethylene), PI (polyimide) and an ABS resin.

As the filler, the foregoing inorganic filler and organic filler can beused singly or as an arbitrary mixture of two or more kinds thereof.

[Surfactant]

As the surfactant, any material is useful so far as it is able todisperse the filler therein, and suitable examples thereof includehydrocarbon based surfactants and silicone based surfactants. Nonionichydrocarbon based surfactants and nonionic silicone based surfactantsare especially desirable because they do not generate an ion.

Examples of the hydrocarbon based surfactant include nonionichydrocarbon based surfactants such as polyoxyethylene alkyl ethers,polyoxyethylene alkyl phenyl ethers, alkylpyrrolidones (for example,1-octyl-2-pyrrolidone, etc.), alkyl glucosides, sorbitan fatty acidesters, mono- or diethanolamine fatty acid amides, polyoxyethyleneadducts of alkylamines, ethoxylated tetramethyldodecinediol,tetramethyldecinediol, glycerin fatty acid esters, pentaerythritol fattyacid esters, polyoxyethylene polyoxypropylene glycol, polyethyleneglycol fatty acid esters and fatty acid polyoxyethylene sorbitans.

Examples of the polyoxyethylene alkyl ether include polyoxyethylenelauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleylether.

Also, examples of the polyoxyethylene alkyl phenyl ether includepolyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenylether.

Furthermore, examples of the polyethylene glycol fatty acid esterinclude polyethylene glycol dilaurate and polyethylene glycoldistearate.

On the contrary, examples of the silicone based surfactant includenonionic silicone based surfactants such as dimethyl silicone,aminosilane, acrylsilane, vinylbenzylsilane, vinylbenzylaminosilane,glycidosilane, mercaptosilane, dimethylsilane, polydimethylsiloxane,polyalkoxysiloxanes, hydrodiene-modified siloxanes, vinyl-modifiedsiloxanes, hydroxy-modified siloxanes, amino-modified siloxanes,carboxyl-modified siloxanes, halogenated modified siloxanes,epoxy-modified siloxanes, methacryloxy-modified siloxanes,mercapto-modified siloxanes, fluorine-modified siloxanes, alkylgroup-modified siloxanes, phenyl-modified siloxanes and alkyleneoxide-modified siloxanes.

The foregoing hydrocarbon based surfactant and silicone based surfactantcan be used singly or as an arbitrary mixture of two or more kindsthereof.

Also, a content of the surfactant is preferably from 0.3 to 5.0 parts bymass based on 100 parts by mass of the filler. When the content of thesurfactant falls within the foregoing range, the strength (load) until ashort circuit is generated can be more increased without substantiallylowering the battery characteristics.

2. Second Embodiment

The second nonaqueous electrolyte composition according to the SecondEmbodiment is a composition containing a nonaqueous solvent, anelectrolyte salt, a matrix resin and a filler containing at least analuminum oxide.

Also, the aluminum oxide is an aluminum oxide having an alpha-conversionrate of 80% or more.

Such a nonaqueous electrolyte composition is suitably used for anonaqueous electrolyte secondary battery.

The nonaqueous solvent and the electrolyte salt in the second nonaqueouselectrolyte composition according to the Second Embodiment are the sameas those described above, and therefore, explanations thereof areomitted.

[Matrix Resin]

The matrix resin is not particularly limited so far as it is able toimpregnate therewith or hold therein the foregoing nonaqueous solvent,the foregoing electrolyte salt and the following filler. For example,polymers (that is, homopolymers, copolymers and multi-componentcopolymers) containing, as a constituent component, vinylidene fluoride,hexafluoropropylene, polytetrafluoroethylene, etc. are preferable.Specific examples thereof include polyvinylidene fluoride (PVdF), apolyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP) and apolyvinylidene fluoride-hexafluoropropylene-chlorotrifluoroethylenecopolymer (PVdF-HFP-CTFE).

The matrix resin includes a matrix resin which impregnates therewith orholds therein the foregoing nonaqueous solvent and electrolyte salt,thereby causing swelling, gelation or immobilization. Also, according tothis, the liquid leakage of the nonaqueous electrolyte in the obtainedbattery can be suppressed.

Also, a content of the matrix resin is preferably from 4 to 15% by mass.In the case where the content of the matrix resin is less than 4% bymass, it may be impossible to gelate the nonaqueous electrolytecomposition, and it may be impossible to uniformly hold the fillertherein. On the other hand, in the case where the content of the matrixresin exceeds 15% by mass, there is a possibility that the batterycharacteristics are affected, for example, the energy density isreduced.

[Filler]

The filler is a material containing at least an aluminum oxide (Al₂O₃),with an alpha-conversion rate of the aluminum oxide being 80% or more.In addition to the aluminum oxide having an alpha-conversion rate of 80%or more, the filler may also contain other inorganic filler or organicfiller together therewith.

Such a filler is desirably a ceramic powder in which a concentration ofthe total sum of impurities such as iron, copper, silicon, sodium,magnesium and zirconium (however, in the case where the ceramic powdercontains zirconium oxide, zirconium is excluded; and in the case wherethe ceramic power contains magnesium oxide, magnesium is excluded) isnot more than 100 ppm. In the case where the concentration of the totalsum of the impurities exceeds 100 ppm, there is a concern that the cyclecharacteristic in the battery characteristics is lowered.

Examples of the inorganic filler to be contained together with thealuminum oxide include ceramic powders such as zirconium oxide (ZrO₂),titanium oxide (TiO₂) and magnesium oxide (MgO). These ceramic powderscan be used singly or as an arbitrary mixture of two or more kindsthereof together with the aluminum oxide having an alpha-conversion rateof 80% or more.

On the contrary, the organic filler to be contained together with thealuminum oxide is not particularly limited so far as it has a highstrength in the copresence of a nonaqueous solvent as compared with thematrix resin. Examples thereof include resin powers such as PTFE(polytetrafluoroethylene), PI (polyimide) and an ABS resin. These resinpowders can be used singly or as an arbitrary mixture of two or morekinds thereof together with the aluminum oxide having analpha-conversion rate of 80% or more.

For example, the nonaqueous electrolyte composition may contain, asother component, a surfactant capable of dispersing the foregoing fillertherein.

Suitable examples of such a surfactant include hydrocarbon basedsurfactants and silicone based surfactants. Nonionic hydrocarbon basedsurfactants and nonionic silicone based surfactants are especiallydesirable because they do not generate an ion.

Examples of the hydrocarbon based surfactant include nonionichydrocarbon based surfactants such as polyoxyethylene alkyl ethers,polyoxyethylene alkyl phenyl ethers, alkylpyrrolidones (for example,1-octyl-2-pyrrolidone, etc.), alkyl glucosides, sorbitan fatty acidesters, mono- or diethanolamine fatty acid amides, polyoxyethyleneadducts of alkylamines, ethoxylated tetramethyldodecinediol,tetramethyldecinediol, glycerin fatty acid esters, pentaerythritol fattyacid esters, polyoxyethylene polyoxypropylene glycol, polyethyleneglycol fatty acid esters and fatty acid polyoxyethylene sorbitans.

Examples of the polyoxyethylene alkyl ether include polyoxyethylenelauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleylether.

Also, examples of the polyoxyethylene alkyl phenyl ether includepolyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenylether.

Furthermore, examples of the polyethylene glycol fatty acid esterinclude polyethylene glycol dilaurate and polyethylene glycoldistearate.

On the contrary, examples of the silicone based surfactant includedimethyl silicone, aminosilane, acrylsilane, vinylbenzylsilane,vinylbenzylaminosilane, glycidosilane, mercaptosilane, dimethylsilane,polydimethylsiloxane, polyalkoxysiloxanes, hydrodiene-modifiedsiloxanes, vinyl-modified siloxanes, hydroxy-modified siloxanes,amino-modified siloxanes, carboxyl-modified siloxanes, halogenatedmodified siloxanes, epoxy-modified siloxanes, methacryloxy-modifiedsiloxanes, mercapto-modified siloxanes, fluorine-modified siloxanes,alkyl group-modified siloxanes, phenyl-modified siloxanes and alkyleneoxide-modified siloxanes.

The foregoing hydrocarbon based surfactant and silicone based surfactantcan be used singly or as an arbitrary mixture of two or more kindsthereof.

Also, a content of the surfactant is preferably from 0.3 to 5.0 parts bymass based on 100 parts by mass of the filler. When the content of thesurfactant falls within the foregoing range, the strength (load) until ashort circuit is generated can be more increased without substantiallylowering the battery characteristics.

3. Third or Fourth Embodiment Constitution of Nonaqueous ElectrolyteSecondary Battery

FIG. 1 is an exploded perspective view showing an example of thenonaqueous electrolyte secondary battery according to an embodiment ofthe present invention.

As shown in FIG. 1, this secondary battery is constituted such that abattery element 20 having a positive electrode terminal 11 and anegative electrode terminal 12 installed therein is enclosed in theinside of an exterior member 30 in a film form. The positive electrodeterminal 11 and the negative electrode terminal 12 are led out from theinside toward the outside of the exterior member 30 in, for example, thesame direction, respectively. Each of the positive electrode terminal 11and the negative electrode terminal 12 is, for example, constituted of ametal material such as aluminum (Al), copper (Cu), nickel (Ni) andstainless steel.

The exterior member 30 is, for example, constituted of a rectangularlaminated film prepared by sticking a nylon film, an aluminum foil and apolyethylene film in this order. The exterior member 30 is, for example,disposed such that the side of the polyethylene film and the batteryelement 20 are opposed to each other, and respective outer peripheriesare joined to each other by means of fusion or with an adhesive.

A contact film 31 is inserted between the exterior member 30 and each ofthe positive electrode terminal 11 and the negative electrode terminal12 for the purpose of preventing invasion of the outside air fromoccurring. The contact film 31 is constituted of a material havingadhesion to each of the positive electrode terminal 11 and the negativeelectrode terminal 12. For example, in the case where each of thepositive electrode terminal 11 and the negative electrode terminal 12 isconstituted of the foregoing metal material, it is preferable that eachof the positive electrode terminal 11 and the negative electrodeterminal 12 is constituted of a polyolefin resin such as polyethylene,polypropylene, modified polyethylene and modified polypropylene.

The exterior member 30 may be constituted of a laminated film havingother structure, for example, a metal material-free laminated film, apolymer film such as polypropylene, a metal film or the like, in placeof the foregoing laminated film.

Here, a general constitution of the laminated film can be represented bya laminated structure of (exterior layer)/(metal foil)/(sealant layer)(however, each of the exterior layer and the sealant layer may beconstituted of plural layers). In the foregoing example, the nylon filmis corresponding to the exterior layer; the aluminum foil iscorresponding to the metal foil; and the polyethylene film iscorresponding to the sealant layer.

The metal foil is enough to function as a moisture permeation resistantbarrier film, and not only an aluminum foil but a stainless steel foil,a nickel foil, a plated iron foil and the like can be used. Of these, analuminum foil which is thin, lightweight and excellent in processabilitycan be suitably used.

When a constitution which can be used as the exterior member isenumerated in a mode of (exterior layer)/(metal foil)/(sealant layer),there are exemplified Ny (nylon)/Al (aluminum)/CPP (cast polypropylene),PET (polyethylene terephthalate)/Al/CPP, PET/Al/PET/CPP, PET/Ny/Al/CPP,PET/Ny/Al/Ny/CPP, PET/Ny/Al/Ny/PE (polyethylene), Ny/PE/Al/LLDPE (linearlow density polyethylene), PET/PE/Al/PET/LDPE (low density polyethylene)and PET/Ny/Al/LDPE/CPP.

[Constitution of Battery Element]

FIG. 2 is a schematic sectional view along an II-II line of the batteryelement 20 shown in FIG. 1. In FIG. 2, in the battery element 20, apositive electrode 21 and a negative electrode 22 are located oppositeto each other via a nonaqueous electrolyte composition layer 23 composedof the foregoing first nonaqueous electrolyte composition or secondnonaqueous electrolyte composition and a separator 24 and wound, and anoutermost peripheral part of the battery element 20 is protected by aprotective tape 25.

The first nonaqueous electrolyte composition in the first nonaqueouselectrolyte secondary battery according to the Third Embodiment and thesecond nonaqueous electrolyte composition in the second nonaqueouselectrolyte secondary battery according to the Fourth Embodiment are thesame as those described above, respectively, and therefore, explanationsthereof are omitted.

[Positive Electrode]

Here, for example, the positive electrode 21 has a structure in which apositive electrode active material layer 21B is coated on the bothsurfaces or one surface of a positive electrode collector 21A having apair of surfaces opposing to each other. The positive electrodecollector 21A includes an exposed portion without being provided withthe positive electrode active material layer 21B in one end in alongitudinal direction, and the positive electrode terminal 11 isinstalled in this exposed portion.

The positive electrode collector 21A is, for example, constituted of ametal foil such as an aluminum foil, a nickel foil and a stainless steelfoil.

The positive electrode active material layer 21B contains, as a positiveelectrode active material, any one kind or two or more kinds of apositive electrode material capable of intercalating and deintercalatinga lithium ion and may further contain a conductive agent and a binder,if desired.

Examples of the positive electrode material capable of intercalating anddeintercalating a lithium ion include lithium-free chalcogen compounds(especially, layered compounds and spinel type compounds), for example,oxides such as vanadium oxide (V₂O₅), titanium dioxide (TiO₂) andmanganese dioxide (MnO₂), sulfur (S), disulfides such as iron disulfide(FeS₂), titanium disulfide (TiS₂) and molybdenum disulfide (MoS₂) andniobium diselenide (NbSe₂); lithium-containing compounds containinglithium therein; and conductive polymer compounds, for example,polyaniline, polythiophene, polyacetylene and polypyrrole.

Of these, lithium-containing compounds are preferable because theyinclude a compound capable of obtaining high voltage and high energydensity. Examples of such a lithium-containing compound include complexoxides containing lithium and a transition metal element; and phosphatecompounds containing lithium and a transition metal. From the viewpointof obtaining a higher voltage, those containing cobalt (Co), nickel(Ni), manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), chromium (Cr),vanadium (V), titanium (Ti) or an arbitrary mixture thereof arepreferable.

Such a lithium-containing compound is representatively represented bythe following general formula (1) or (2):

Li_(r)M^(I)O₂  (1)

Li_(s)M^(II)PO₄  (2)

In the formulae (1) and (2), each of M^(I) and M^(II) represents one ormore kinds of a transition metal element; and values of r and s varydepending upon the charge and discharge state of the battery and areusually satisfied with the relationships of (0.05≦r≦1.10) and(0.05≦s≦1.10), respectively. The compound of the formula (1) generallyhas a layered structure; and the compound of the formula (2) generallyhas an olivine structure.

Also, specific examples of the complex oxide containing lithium and atransition metal element include a lithium cobalt complex oxide(LiCoO₂); a lithium nickel complex oxide (LiNiO₂) and a solid solutionthereof (Li(Ni_(t)Co_(u)Mn_(v))O₂ (0<t<1, 0<u<1, 0<v<1 and (t+u+v)=1));a lithium nickel cobalt complex oxide (LiNi_(1-w)Co_(w)O₂ (0<w<1)); anda lithium manganese complex oxide having a spinel type structure(LiMn₂O₄) and a solid solution thereof (Li(Mn_(2-x)Ni_(y))O₄ (0<x<2 and0<y<2).

Specific examples of the phosphate compound containing lithium and atransition metal element include a lithium iron phosphate compoundhaving an olivine structure (LiFePO₄) and a lithium iron manganesephosphate compound (LiFe_(1-z)Mn_(z)PO₄ (0<z<1)).

The conductive agent is not particularly limited so far as it is able toimpart conductivity to the positive active material upon being mixed inan appropriate amount. Examples thereof include carbon materials such asgraphite, carbon black and ketjen black. These materials are used singlyor in admixture of two or more kinds thereof. Also, in addition to thecarbon material, a metal material or a conductive polymer material orthe like may be used so far as it is a material having conductivity.

As the binder, known binders which are usually used in a positiveelectrode mixture of a battery of this type are useful. Preferredexamples of the binder include fluorine based polymers such as polyvinylfluoride, polyvinylidene fluoride and polytetrafluoroethylene; andsynthetic rubbers such as a styrene-butadiene based rubber, a fluorinebased rubber and an ethylene-propylene-diene rubber. These materials areused singly or in admixture of two or more kinds thereof.

[Negative Electrode]

On the contrary, similar to the positive electrode 21, the negativeelectrode 22 has, for example, a structure in which a negative electrodeactive material layer 22B is provided on the both surfaces or onesurface of a negative electrode collector 22A having a pair of surfacesopposing to each other. The negative electrode collector 22A includes anexposed portion without being provided with the negative electrodeactive material layer 22B in one end in a longitudinal direction, andthe negative electrode terminal 12 is installed in this exposed portion.

The negative electrode collector 22A is, for example, constituted of ametal foil such as a copper foil, a nickel foil and a stainless steelfoil.

The negative electrode active material layer 22B contains, as a negativeelectrode active material, any one kind or two or more kinds of anegative electrode material capable of intercalating and deintercalatinga lithium ion and metallic lithium and may further contain a conductiveagent and a binder, if desired.

Examples of the negative electrode material capable of intercalating anddeintercalating a lithium ion include carbon materials, metal oxides andpolymer compounds.

Examples of the carbon material include hardly graphitized carbonmaterials, artificial graphite materials and graphite based materials.More specific examples thereof include pyrolytic carbons, cokes,graphites, vitreous carbons, organic polymer compound burned materials,carbon fibers, active carbon and carbon black. Of these, examples of thecoke include pitch coke, needle coke and petroleum coke. The organicpolymer compound burned material as referred to herein is a materialobtained through carbonization by burning a polymer material, forexample, phenol resins and furan resins at an appropriate temperature.

Also, examples of the metal oxide include iron oxide, ruthenium oxideand molybdenum oxide; and examples of the polymer material includepolyacetylene and polypyrrole.

Furthermore, examples of the negative electrode material capable ofintercalating and deintercalating a lithium ion include materialscontaining, as a constituent element, at least one of metal elements andsemi-metal elements capable of forming an alloy together with lithium.This negative electrode material may be a simple substance, an alloy ora compound of a metal element or a semi-metal element. Also, a materialhaving one or two or more kinds of a phase in at least a part thereofmay be used.

In an embodiment according to the present invention, the alloy alsoincludes an alloy containing one or two or more kinds of a metal elementand one or two or more kinds of a semi-metal element in addition toalloys composed of two or more kinds of a metal element. Also, the alloymay contain a non-metal element. Examples of its texture include a solidsolution, a eutectic (eutectic mixture), an intermetallic compound andone in which two or more kinds thereof coexist.

Examples of such a metal element or semi-metal element include tin (Sn),lead (Pb), magnesium (Mg), aluminum, indium (In), silicon (Si), zinc(Zn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium (Ge), arsenic(As), silver (Ag), hafnium (Hf), zirconium (Zr) and yttrium (Y).

Above all, a metal element or a semi-metal element belonging to theGroup 14 of the long form of the periodic table is preferable; andsilicon and tin are especially preferable. This is because silicon andtin have large capability to intercalate and deintercalate lithium andare able to obtain a high energy density.

Examples of alloys of tin include alloys containing, as a secondconstituent element other than tin, at least one member selected fromthe group consisting of silicon, magnesium, nickel, copper, iron,cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth,antimony and chromium (Cr).

Examples of alloys of silicon include alloys containing, as a secondconstituent element other than silicon, at least one member selectedfrom the group consisting of tin, magnesium, nickel, copper, iron,cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth,antimony and chromium.

Examples of compounds of tin or silicon include compounds containingoxygen (O) or carbon (C), and these compounds may contain the foregoingsecond constituent element in addition to tin or silicon.

Furthermore, the negative electrode material may be an element capableof forming a complex oxide with lithium, such as titanium. As a matterof course, metallic lithium may be deposited and dissolved, or magnesiumor aluminum other than lithium can be deposited and dissolved.

As the conductive agent and the binder, the same materials as those usedin the positive electrode are useful.

[Separator]

Also, the separator 24 is, for example, constituted of an insulatingthin film having large ion permeability and prescribed mechanicalstrength, such as a porous film composed of a polyolefin based syntheticresin (for example, polypropylene, polyethylene, etc.) and a porous filmcomposed of an inorganic material (for example, a ceramic-made nonwovenfabric, etc.), and may have a structure in which two or more kinds ofsuch a porous film are laminated. In particular, one including apolyolefin based porous film is suitable because it is excellent inseparability between the positive electrode 21 and the negativeelectrode 22 and is able to more reduce an internal short circuit or alowering of an open-circuit voltage.

[Preparation of Nonaqueous Electrolyte Secondary Battery]

Next, an example of a manufacturing method of the foregoing nonaqueouselectrolyte secondary battery is described.

First of all, the positive electrode 21 is prepared. For example, in thecase of using a granular positive electrode active material, thepositive electrode active material is mixed with a conductive agent anda binder, if desired, to prepare a positive electrode mixture, which isthen dispersed in a dispersion medium such as N-methyl-2-pyrrolidone toprepare a positive electrode mixture slurry.

Subsequently, this positive electrode mixture slurry is coated on thepositive electrode collector 21A, dried and then compression molded toform the positive electrode active material layer 21B.

Also, the negative electrode 22 is prepared. For example, in the case ofusing a granular negative electrode active material, the negativeelectrode active material is mixed with a conductive agent and a binder,if desired, to prepare a negative electrode mixture, which is thendispersed in a dispersion medium such as N-methyl-2-pyrrolidone toprepare a negative electrode mixture slurry. Thereafter, this negativeelectrode mixture slurry is coated on the negative electrode collector22A, dried and then compression molded to form the negative electrodeactive material layer 22B.

Subsequently, not only the positive electrode terminal 11 is installedin the positive electrode 21, but the negative electrode terminal 12 isinstalled in the negative electrode 22. Thereafter, the negativeelectrode 22, the separator 24, the positive electrode 21 and theseparator 24 are successively laminated and wound, and the protectivetape 25 is allowed to adhere to an outermost peripheral part of thewound laminate, thereby forming a wound electrode body. Furthermore,this wound electrode body is interposed between laminated films as anexample of the exterior member 30, and the outer edges exclusive of oneside are subjected to heat fusion to form a bag.

Thereafter, the foregoing nonaqueous electrolyte composition is preparedand injected into the inside of the wound electrode body from an openingof the laminated film, and the opening of the laminated film is thensubjected to heat fusion and enclosed therein. According to this, thenonaqueous electrolyte composition layer 23 is formed, therebycompleting the nonaqueous electrolyte secondary battery shown in FIGS. 1and 2.

This nonaqueous electrolyte secondary battery may also be manufacturedin the following manner.

For example, the foregoing nonaqueous electrolyte composition is notinjected after preparing the wound electrode body; but the nonaqueouselectrolyte secondary battery may be prepared by coating the nonaqueouselectrolyte composition on each of the positive electrode 21 and thenegative electrode 22 or the separator 24 and winding to prepare a woundelectrode body and then enclosing the wound electrode body in the insideof the laminated film.

Also, for example, the nonaqueous electrolyte composition layer 23 maybe formed by coating a solution of a monomer or polymer of the matrixpolymer (for example, the foregoing polyvinylidene fluoride, etc.) oneach of the negative electrode 21 and the positive electrode 22 or theseparator 24 and winding to prepare a wound electrode body, housing thewound electrode body in the inside of the exterior member 30 composed ofa laminated film and then injecting other component of the foregoingnonaqueous electrolyte composition thereinto.

However, what the monomer is polymerized in the inside of the exteriormember 30 is preferable because welding properties between thenonaqueous electrolyte composition layer 23 and the separator 24 areenhanced, thereby enabling one to make the internal resistance low.Also, why the nonaqueous electrolyte composition or the like is injectedinto the inside of the exterior member 30 to form the nonaqueouselectrolyte composition layer 23 is preferable because the nonaqueouselectrolyte secondary battery can be simply manufactured by a smallernumber of steps.

[Explanation of Action]

In the nonaqueous electrolyte secondary battery which has been describedabove, when charged, a lithium ion is deintercalated from the positiveelectrode active material layer 21B and intercalated into the negativeelectrode active material layer 22B via the nonaqueous electrolytecomposition layer 23. When discharged, a lithium ion is deintercalatedfrom the negative electrode active material layer 22B and intercalatedinto the positive electrode active material layer 21B via the nonaqueouselectrolyte composition layer 23.

EXAMPLES

The present invention is hereunder described in more detail withreference to the following Examples and Comparative Examples, but itshould not be construed that the present invention is limited to onlythese Examples and Comparative Examples.

Specifically, operations described in each of the following Examples andComparative Examples were performed, thereby preparing the nonaqueouselectrolyte secondary battery shown in FIGS. 1 and 2, and performancesthereof were evaluated.

Example 1-1-1 Preparation of Positive Electrode

First of all, 91 parts by mass of a lithium cobalt complex oxide(LiCoO₂) as a positive electrode active material, 6 parts by mass ofgraphite as a conductive agent and 10 parts by mass of polyvinylidenefluoride (PVdF) as a binder were uniformly mixed, and the mixture wasdispersed in N-methyl-2-pyrrolidone (NMP) to obtain a positive electrodemixture slurry.

Subsequently, the obtained positive electrode mixture slurry wasuniformly coated on the both surfaces of a 20 μm-thick strip-shapedaluminum foil serving as a positive electrode collector and dried toform a positive electrode active material layer. This was cut into ashape having a size of 38 mm in width and 700 mm in length, therebypreparing a positive electrode. A positive electrode terminal wasfurther installed in the positive electrode.

(Preparation of Negative Electrode)

Next, 90 parts by mass of artificial graphite as a negative electrodeactive material and 10 parts by mass of PVdF as a binder were uniformlymixed, and the mixture was dispersed in NMP to obtain a negativeelectrode mixture slurry.

Subsequently, the obtained negative electrode mixture slurry wasuniformly coated on the both surfaces of a 10 μm-thick strip-shapedcopper foil serving as a negative electrode collector and dried to forma negative electrode mixture layer. This was cut into a shape having asize of 40 mm in width and 650 mm in length, thereby preparing anegative electrode. A negative electrode terminal was further installedin the negative electrode.

(Preparation of Nonaqueous Electrolyte Composition)

Also, a composition prepared by mixing 90 parts by mass of a nonaqueouselectrolytic solution, 10 parts by mass of a polyvinylidenefluoride-hexafluoropropylene copolymer (PVdF/HFP=93.1/6.9 (mass ratio))as a matrix resin, 10 parts by mass of an aluminum oxide (concentrationof impurities: 55 ppm, alpha-conversion rate: 90%) as a filler and 0.2parts by mass, based on 100 parts by mass of the filler, of ahydrocarbon based surfactant (nonionic polyoxyethylene lauryl ether) asa surfactant and dispersing the mixture was used as a nonaqueouselectrolyte composition.

A solution prepared by dissolving lithium hexafluorophosphate (LiPF₆) asan electrolyte salt in a concentration of 0.8 moles/kg in a nonaqueoussolvent prepared by mixing ethylene carbonate and propylene carbonate ina proportion of ethylene carbonate to propylene carbonate of 6/4 (massratio) was used as the nonaqueous electrolytic solution.

Also, at that time, a dispersing time was 30 minutes.

(Preparation of Nonaqueous Electrolyte Secondary Battery)

The obtained positive electrode and negative electrode were each coatedwith the obtained nonaqueous electrolyte composition, laminated via a 20μm-thick microporous polyethylene film serving as a separator and thenwound. The wound laminate was sealed in an exterior material composed ofan aluminum laminated film, thereby obtaining a nonaqueous electrolytesecondary battery of this Example.

A part of the specification of the obtained nonaqueous electrolytesecondary battery is shown in Table 1.

Examples 1-1-2 to 1-1-5 and Comparative Examples 1-1-1 and 1-1-2

The same operations as in Example 1-1-1 were repeated, except that inthe preparation of a nonaqueous electrolyte composition, a part of thespecification was changed as shown in Table 1, thereby obtainingnonaqueous electrolyte secondary batteries of the respective Examplesand Comparative Examples.

TABLE 1 Surfactant Filler Addition Alpha- Short- Cycle amountConcentration conversion circuit characteristic Dispersing Kind (partsby of impurities Kind rate load (500 cycles) OCV time (—) mass) (ppm)(—) (%) (N) (%) (V) (min) Example Hydrocarbon 0.2 55 Al₂O₃ 90 1050 864.115 30 1-1-1 based Example Hydrocarbon 0.3 55 Al₂O₃ 90 1070 86 4.11910 1-1-2 based Example Hydrocarbon 1.0 55 Al₂O₃ 90 1080 86 4.117 101-1-3 based Example Hydrocarbon 5.0 55 Al₂O₃ 90 1090 84 4.113 10 1-1-4based Example Hydrocarbon 6.0 55 Al₂O₃ 90 1085 80 4.111 10 1-1-5 basedComparative — — — — — 750 86 4.12 — Example 1-1-1 ComparativeHydrocarbon 1.0 — — — 750 86 4.11 10 Example based 1-1-2

Examples 1-2-1 to 1-2-5 and Comparative Examples 1-1-1 and 1-1-3

The same operations as in Example 1-1-1 were repeated, except that inthe preparation of a nonaqueous electrolyte composition, apart of thespecification was changed as shown in Table 2, thereby obtainingnonaqueous electrolyte secondary batteries of the respective Examplesand Comparative Examples.

In the following Examples and Comparative Example, 3-methacrylopropyltriethoxysilane was used as the silicone based surfactant.

TABLE 2 Surfactant Filler Addition Alpha- Short- Cycle amountConcentration conversion circuit characteristic Dispersing Kind (partsby of impurities Kind rate load (500 cycles) OCV time (—) mass) (ppm)(—) (%) (N) (%) (V) (min) Example Silicone 0.2 55 Al₂O₃ 90 1050 86 4.11530 1-2-1 based Example Silicone 0.3 55 Al₂O₃ 90 1070 86 4.119 10 1-2-2based Example Silicone 1.0 55 Al₂O₃ 90 1080 86 4.117 10 1-2-3 basedExample Silicone 5.0 55 Al₂O₃ 90 1090 84 4.113 10 1-2-4 based ExampleSilicone 6.0 55 Al₂O₃ 90 1090 80 4.11 10 1-2-5 based Comparative — — — —— 750 86 4.12 — Example 1-1-1 Comparative Silicone 1.0 — — — 750 86 4.1110 Example based 1-1-3

Examples 1-3-1 to 1-3-5 and Comparative Examples 1-1-1, 1-1-2 and 1-1-4to 1-1-7

The same operations as in Example 1-1-1 were repeated, except that inthe preparation of a nonaqueous electrolyte composition, a part of thespecification was changed as shown in Table 3, thereby obtainingnonaqueous electrolyte secondary batteries of the respective Examplesand Comparative Examples.

TABLE 3 Surfactant Filler Addition Alpha- Short- Cycle amountConcentration conversion circuit characteristic Dispersing Kind (partsby of impurities Kind rate load (500 cycles) OCV time (—) mass) (ppm)(—) (%) (N) (%) (V) (min) Example Hydrocarbon 0.2 55 ZrO₂ — 1040 844.116 30 1-3-1 based Example Hydrocarbon 0.3 55 ZrO₂ — 1060 86 4.119 101-3-2 based Example Hydrocarbon 1.0 55 ZrO₂ — 1070 86 4.117 10 1-3-3based Example Hydrocarbon 5.0 55 ZrO₂ — 1080 84 4.113 10 1-3-4 basedExample Hydrocarbon 6.0 55 ZrO₂ — 1080 80 4.11 10 1-3-5 basedComparative — — — — — 750 86 4.12 — Example 1-1-1 ComparativeHydrocarbon 1.0 — — — 750 86 4.11 10 Example based 1-1-2 Comparative — —20 ZrO₂ — 1040 86 4.12 30 Example 1-1-4 Comparative — — 55 ZrO₂ — 104086 4.116 30 Example 1-1-5 Comparative — — 100 ZrO₂ — 1040 86 4.11 30Example 1-1-6 Comparative — — 150 ZrO₂ — 1040 85 4.095 30 Example 1-1-7

Examples 1-4-1 to 1-4-5 and Comparative Examples 1-1-1, 1-1-3 and 1-1-4to 1-1-7

The same operations as in Example 1-1-1 were repeated, except that inthe preparation of a nonaqueous electrolyte composition, a part of thespecification was changed as shown in Table 4, thereby obtainingnonaqueous electrolyte secondary batteries of the respective Examplesand Comparative Examples.

TABLE 4 Surfactant Filler Addition Alpha- Short- Cycle amountConcentration conversion circuit characteristic Dispersing Kind (partsby of impurities Kind rate load (500 cycles) OCV time (—) mass) (ppm)(—) (%) (N) (%) (V) (min) Example Silicone 0.2 55 ZrO₂ — 1030 86 4.11530 1-4-1 based Example Silicone 0.3 55 ZrO₂ — 1050 86 4.119 10 1-4-2based Example Silicone 1.0 55 ZrO₂ — 1070 85 4.117 10 1-4-3 basedExample Silicone 5.0 55 ZrO₂ — 1080 84 4.113 10 1-4-4 based ExampleSilicone 6.0 55 ZrO₂ — 1080 80 4.109 30 1-4-5 based Comparative — — — —— 750 86 4.12 — Example 1-1-1 Comparative Silicone 1.0 — — — 750 86 4.1110 Example based 1-1-3 Comparative — — 20 ZrO₂ — 1040 86 4.12 30 Example1-1-4 Comparative — — 55 ZrO₂ — 1040 86 4.116 30 Example 1-1-5Comparative — — 100 ZrO₂ — 1040 86 4.11 30 Example 1-1-6 Comparative — —150 ZrO₂ — 1040 85 4.095 30 Example 1-1-7

Examples 1-5-1 to 1-5-3 and Comparative Examples 1-1-1, 1-1-2 and 1-1-8to 1-1-10

The same operations as in Example 1-1-1 were repeated, except that inthe preparation of a nonaqueous electrolyte composition, a part of thespecification was changed as shown in Table 5, thereby obtainingnonaqueous electrolyte secondary batteries of the respective Examplesand Comparative Examples.

TABLE 5 Surfactant Filler Addition Alpha- Short- Cycle amountConcentration conversion circuit characteristic Dispersing Kind (partsby of impurities Kind rate load (500 cycles) OCV time (—) mass) (ppm)(—) (%) (N) (%) (V) (min) Example Hydrocarbon 0.3 55 TiO₂ — 1060 864.119 10 1-5-1 based Example Hydrocarbon 1.0 55 TiO₂ — 1070 85 4.117 101-5-2 based Example Hydrocarbon 5.0 55 TiO₂ — 1080 83 4.113 10 1-5-3based Comparative — — — — — 750 86 4.12 — Example 1-1-1 ComparativeHydrocarbon 1.0 — — — 750 86 4.11 10 Example based 1-1-2 Comparative — —20 TiO₂ — 1050 86 4.12 30 Example 1-1-8 Comparative — — 55 TiO₂ — 105086 4.116 30 Example 1-1-9 Comparative — — 100 TiO₂ — 1050 86 4.11 30Example 1-1-10

Examples 1-6-1 to 1-6-3 and Comparative Examples 1-1-1, 1-1-3 and 1-1-8to 1-1-10

The same operations as in Example 1-1-1 were repeated, except that inthe preparation of a nonaqueous electrolyte composition, a part of thespecification was changed as shown in Table 6, thereby obtainingnonaqueous electrolyte secondary batteries of the respective Examplesand Comparative Examples.

TABLE 6 Surfactant Filler Addition Alpha- Short- Cycle amountConcentration conversion circuit characteristic Dispersing Kind (partsby of impurities Kind rate load (500 cycles) OCV time (—) mass) (ppm)(—) (%) (N) (%) (V) (min) Example Silicone 0.3 55 TiO₂ — 1050 85 4.11910 1-6-1 based Example Silicone 1.0 55 TiO₂ — 1070 85 4.117 10 1-6-2based Example Silicone 5.0 55 TiO₂ — 1080 84 4.113 10 1-6-3 basedComparative — — — — — 750 86 4.12 — Example 1-1-1 Comparative Silicone1.0 — — — 750 86 4.11 10 Example based 1-1-3 Comparative — — 20 TiO₂ —1050 86 4.12 30 Example 1-1-8 Comparative — — 55 TiO₂ — 1050 86 4.116 30Example 1-1-9 Comparative — — 100 TiO₂ — 1050 86 4.11 30 Example 1-1-10

Examples 1-7-1 to 1-7-3 and Comparative Examples 1-1-1, 1-1-2 and 1-1-11to 1-1-13

The same operations as in Example 1-1-1 were repeated, except that inthe preparation of a nonaqueous electrolyte composition, a part of thespecification was changed as shown in Table 7, thereby obtainingnonaqueous electrolyte secondary batteries of the respective Examplesand Comparative Examples.

TABLE 7 Surfactant Filler Addition Alpha- Short- Cycle amountConcentration conversion circuit characteristic Dispersing Kind (partsby of impurities Kind rate load (500 cycles) OCV time (—) mass) (ppm)(—) (%) (N) (%) (V) (min) Example Hydrocarbon 0.3 55 MgO — 1060 86 4.11910 1-7-1 based Hydrocarbon Example 1.0 55 MgO — 1070 86 4.117 10 1-7-2based Example Hydrocarbon 5.0 55 MgO — 1080 84 4.113 10 1-7-3 basedComparative — — — — — 750 86 4.12 — Example 1-1-1 ComparativeHydrocarbon 1.0 — — — 750 86 4.11 10 Example based 1-1-2 Comparative — —20 MgO — 1040 86 4.12 30 Example 1-1-11 Comparative — — 55 MgO — 1040 864.116 30 Example 1-1-12 Comparative — — 100 MgO — 1040 86 4.11 30Example 1-1-13

Examples 1-8-1 to 1-8-3 and Comparative Examples 1-1-1, 1-1-3 and 1-1-11to 1-1-13

The same operations as in Example 1-1-1 were repeated, except that inthe preparation of a nonaqueous electrolyte composition, a part of thespecification was changed as shown in Table 8, thereby obtainingnonaqueous electrolyte secondary batteries of the respective Examplesand Comparative Examples.

TABLE 8 Surfactant Filler Addition Alpha- Short- Cycle amountConcentration conversion circuit characteristic Dispersing Kind (partsby of impurities Kind rate load (500 cycles) OCV time (—) mass) (ppm)(—) (%) (N) (%) (V) (min) Example Silicone 0.3 55 MgO — 1050 86 4.119 101-8-1 based Example Silicone 1.0 55 MgO — 1070 86 4.117 10 1-8-2 basedExample Silicone 5.0 55 MgO — 1080 84 4.113 10 1-8-3 based Comparative —— — — — 750 86 4.12 — Example 1-1-1 Comparative Silicone 1.0 — — — 75086 4.11 10 Example based 1-1-3 Comparative — — 20 MgO — 1040 86 4.12 30Example 1-1-11 Comparative — — 55 MgO — 1040 86 4.116 30 Example 1-1-12Comparative — — 100 MgO — 1040 86 4.11 30 Example 1-1-13

Example 2-1-1 Preparation of Positive Electrode

First of all, 91 parts by mass of a lithium cobalt complex oxide(LiCoO₂) as a positive electrode active material, 6 parts by mass ofgraphite as a conductive agent and 10 parts by mass of polyvinylidenefluoride (PVdF) as a binder were uniformly mixed, and the mixture wasdispersed in N-methyl-2-pyrrolidone (NMP) to obtain a positive electrodemixture slurry.

Subsequently, the obtained positive electrode mixture slurry wasuniformly coated on the both surfaces of a 20 μm-thick strip-shapedaluminum foil serving as a positive electrode collector and dried toform a positive electrode active material layer. This was cut into ashape having a size of 38 mm in width and 700 mm in length, therebypreparing a positive electrode. A positive electrode terminal wasfurther installed in the positive electrode.

(Preparation of Negative Electrode)

Next, 90 parts by mass of artificial graphite as a negative electrodeactive material and 10 parts by mass of PVdF as a binder were uniformlymixed, and the mixture was dispersed in NMP to obtain a negativeelectrode mixture slurry.

Subsequently, the obtained negative electrode mixture slurry wasuniformly coated on the both surfaces of a 10 μm-thick strip-shapedcopper foil serving as a negative electrode collector and dried to forma negative electrode mixture layer. This was cut into a shape having asize of 40 mm in width and 650 mm in length, thereby preparing anegative electrode. A negative electrode terminal was further installedin the negative electrode.

(Preparation of Nonaqueous Electrolyte Composition)

Also, a composition prepared by mixing 90 parts by mass of a nonaqueouselectrolytic solution, 10 parts by mass of a polyvinylidenefluoride-hexafluoropropylene copolymer (PVdF/HFP=93.1/6.9 (mass ratio))as a matrix resin and 10 parts by mass of an aluminum oxide(concentration of impurities: 20 ppm, alpha-conversion rate: 90%) as afiller and dispersing the mixture was used as a nonaqueous electrolytecomposition.

A solution prepared by dissolving lithium hexafluorophosphate (LiPF₆) asan electrolyte salt in a concentration of 0.8 moles/kg in a nonaqueoussolvent prepared by mixing ethylene carbonate and propylene carbonate ina proportion of ethylene carbonate to propylene carbonate of 6/4 (massratio) was used as the nonaqueous electrolytic solution.

Also, at that time, a dispersing time was 30 minutes.

(Preparation of Nonaqueous Electrolyte Secondary Battery)

The obtained positive electrode and negative electrode were each coatedwith the obtained nonaqueous electrolyte composition, laminated via a 20μm-thick microporous polyethylene film serving as a separator and thenwound. The wound laminate was sealed in an exterior material composed ofan aluminum laminated film, thereby obtaining a nonaqueous electrolytesecondary battery of this Example.

A part of the specification of the obtained nonaqueous electrolytesecondary battery is shown in Table 9.

Examples 2-1-2 to 2-1-6 and Comparative Example 2-1-1

The same operations as in Example 2-1-1 were repeated, except that inthe preparation of a nonaqueous electrolyte composition, a part of thespecification was changed as shown in Table 9, thereby obtainingnonaqueous electrolyte secondary batteries of the respective Examplesand Comparative Example.

TABLE 9 Surfactant Filler Addition Alpha- Short- Cycle amountConcentration conversion circuit characteristic Dispersing Kind (partsby of impurities Kind rate load (500 cycles) OCV time (—) mass) (ppm)(—) (%) (N) (%) (V) (min) Example 2-1-1 — — 20 Al₂O₃ 90 1050 86 4.12 30Example 2-1-2 — — 55 Al₂O₃ 90 1050 86 4.116 30 Example 2-1-3 — — 100Al₂O₃ 90 1050 86 4.11 30 Example 2-1-4 — — 150 Al₂O₃ 90 1050 85 4.095 30Example 2-1-5 — — 55 Al₂O₃ 80 1040 84 4.11 30 Example 2-1-6 — — 55 Al₂O₃100 1050 87 4.116 30 Comparative — — 55 Al₂O₃ 75 1050 80 4.108 30Example 2-1-1

[Evaluation of Performances]

The thus obtained respective batteries of the respective Examples andComparative Examples were evaluated with respect to the followingperformances, and the obtained results are also shown in Tables 1 to 9.

(Short-Circuit Load)

A cell center was pressurized at a rate of 3 mm/min by a SUS-made rodhaving a diameter of 10 mm, a tip angle of 45° and R=4 mm, and a loadimpressed to the cell until a short circuit was generated was measured.A value of 1,000 N or more is considered to be favorable.

(Cycle Characteristic)

An operation of charging the battery at 4.2 V and 1 C for 3 hours andthen discharging it to 3.0 V at 1 C was defined as one cycle, and thisoperation was repeated. It is desirable that a retention rate after 500cycles shows 80% or more.

(Open-Circuit Voltage (OCV))

The battery was charged at 4.2 V and 1 C for 3 hours and then allowed tostand in an atmosphere at 80° C. for 4 days. After allowing the batteryto stand, its open-circuit voltage was measured. It is desirable thatthe open-circuit voltage after 4 days shows 4.1 V or more.

It is noted from Table 1 that Examples 1-1-1 to 1-1-5 falling within theclaimed scope enhance the short-circuit load without remarkably loweringthe battery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1 and 1-1-2 falling outside theclaimed scope. In particular, it is noted that Examples 1-1-2 to 1-1-4more enhance the short-circuit load without substantially lowering thebattery characteristics such as the cycle characteristic and OCV.

It is noted from Table 2 that Examples 1-2-1 to 1-2-5 falling within theclaimed scope enhance the short-circuit load without remarkably loweringthe battery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1 and 1-1-3 falling outside theclaimed scope. In particular, it is noted that Examples 1-2-2 to 1-2-4more enhance the short-circuit load without substantially lowering thebattery characteristics such as the cycle characteristic and OCV.

It is noted from Table 3 that Examples 1-3-1 to 1-3-5 falling within theclaimed scope enhance the short-circuit load without remarkably loweringthe battery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1 and 1-1-2 falling outside theclaimed scope. In particular, it is noted that Examples 1-3-2 to 1-3-4more enhance the short-circuit load without substantially lowering thebattery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1, 1-1-2 and 1-1-4 to 1-1-7.

It is noted from Table 4 that Examples 1-4-1 to 1-4-5 falling within theclaimed scope enhance the short-circuit load without remarkably loweringthe battery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1 and 1-1-3 falling outside theclaimed scope. In particular, it is noted that Examples 1-4-2 to 1-4-4more enhance the short-circuit load without substantially lowering thebattery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1, 1-1-3 and 1-1-4 to 1-1-7.

It is noted from Table 5 that Examples 1-5-1 to 1-5-3 falling within theclaimed scope enhance the short-circuit load without remarkably loweringthe battery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1 and 1-1-2 falling outside theclaimed scope. In particular, it is noted that Examples 1-5-1 to 1-5-3more enhance the short-circuit load without substantially lowering thebattery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1, 1-1-2 and 1-1-8 to 1-1-10.

It is noted from Table 6 that Examples 1-6-1 to 1-6-3 falling within theclaimed scope enhance the short-circuit load without remarkably loweringthe battery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1 and 1-1-3 falling outside theclaimed scope. In particular, it is noted that Examples 1-6-1 to 1-6-3more enhance the short-circuit load without substantially lowering thebattery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1, 1-1-3 and 1-1-8 to 1-1-10.

It is noted from Table 7 that Examples 1-7-1 to 1-7-3 falling within theclaimed scope enhance the short-circuit load without remarkably loweringthe battery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1 and 1-1-2 falling outside theclaimed scope. In particular, it is noted that Examples 1-7-1 to 1-7-3more enhance the short-circuit load without substantially lowering thebattery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1, 1-1-2 and 1-1-11 to 1-1-13.

It is noted from Table 8 that Examples 1-8-1 to 1-8-3 falling within theclaimed scope enhance the short-circuit load without remarkably loweringthe battery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1 and 1-1-3 falling outside theclaimed scope. In particular, it is noted that Examples 1-8-1 to 1-8-3more enhance the short-circuit load without substantially lowering thebattery characteristics such as the cycle characteristic and OCV ascompared with Comparative Examples 1-1-1, 1-1-3 and 1-1-11 to 1-1-13.

It is noted from Table 9 that Examples 2-1-1 to 2-1-6 falling within theclaimed scope enhance the short-circuit load without remarkably loweringthe battery characteristics such as the cycle characteristic and OCV ascompared with Comparative Example 2-1-1 falling outside the claimedscope.

Also, it is noted from Table 9 that the alpha-conversion rate is morepreferably 90% or more. Furthermore, it is noted from Table 9 that theconcentration of impurities is more preferably not more than 100 ppm.

While the present invention has been described with reference to theembodiments and working examples, it should not be construed that thepresent invention is limited to the foregoing embodiments and workingexamples, but various modifications can be made within the gist of thepresent invention.

For example, in the foregoing embodiments, while the case where thebattery element 20 having the positive electrode 21 and the negativeelectrode 22 laminated and wound therein is provided has been described,the present invention is also applicable to the case where aplate-shaped battery element having a pair of a positive electrode and anegative electrode laminated therein or a battery element of a laminatetype in which a plurality of positive electrodes and negative electrodesare laminated is provided.

Furthermore, as described previously, though the present invention isconcerned with a battery using lithium as an electrode reactant, thetechnical thought of the present invention is also applicable to thecase of using other alkali metal such as sodium (Na) and potassium (K),an alkaline earth metal such as magnesium (Mg) and calcium (Ca), orother light metal such as aluminum.

The present application contains subject matter related to thatdisclosed in Japanese Priority Patent Application JP 2009-108064 filedin the Japan Patent Office on Apr. 27, 2009, the entire contents ofwhich is hereby incorporated by reference.

It should be understood by those skilled in the art that variousmodifications, combinations, sub-combinations and alterations may occurdepending on design requirements and other factors insofar as they arewithin the scope of the appended claims or the equivalents thereof.

What is claimed is:
 1. A nonaqueous electrolyte composition comprising:a nonaqueous solvent; an electrolyte salt; a matrix resin; a filler; anda surfactant that disperses the filler within the nonaqueous electrolytecomposition.
 2. The nonaqueous electrolyte composition according toclaim 1, wherein the surfactant is a surfactant containing a hydrocarbonbased surfactant.
 3. The nonaqueous electrolyte composition according toclaim 1, wherein the surfactant is contained in a proportion of from 0.3to 5.0 parts by mass based on 100 parts by mass of the filler.
 4. Thenonaqueous electrolyte composition according to claim 1, wherein, thefiller in the filler, a concentration of the total sum of iron, copper,silicon, sodium, magnesium and zirconium, provided that in the casewhere the ceramic powder contains zirconium oxide, zirconium is excludedand that in the case where the ceramic power contains magnesium oxide,magnesium is excluded, is not more than 100 ppm.
 5. The nonaqueouselectrolyte composition according to claim 1, wherein the filler furthercomprises at least one member selected from the group consisting ofzirconium oxide, titanium oxide and magnesium oxide.
 6. A nonaqueouselectrolyte secondary battery comprising: a positive electrode; anegative electrode; a separator; and a nonaqueous electrolytecomposition, wherein the nonaqueous electrolyte composition contains anonaqueous solvent, an electrolyte salt, a matrix resin, a filler, and asurfactant that disperses the filler within the nonaqueous electrolytecomposition.
 7. The nonaqueous electrolyte composition according toclaim 2, wherein the hydrocarbon based surfactant is nonionic.
 8. Thenonaqueous electrolyte composition according to claim 1, wherein thenonaqueous solvent is contained in a proportion of from 70 to 90 partsby mass based on 100 parts by mass of the nonaqueous electrolytecomposition.
 9. The nonaqueous electrolyte composition according toclaim 1, wherein the electrolyte salt is contained in a proportion offrom 10 to 30 parts by mass based on 100 parts by mass of the nonaqueouselectrolyte composition.
 10. The nonaqueous electrolyte compositionaccording to claim 1, wherein the matrix resin is contained in aproportion of from 4 to 15 parts by mass based on 100 parts by mass ofthe nonaqueous electrolyte composition.